Stabilization of oil-containing compositions with reductones



United States Patent Ofificc 2,805,794 Patented Sept. 17, 1957 STABILIZATION F OIL-CONTAINING COMPO- SITIONS WITH REDUCTONES John E. Hodge, Peoria, and Cyril D. Evans, Peoria Heights, Ill., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application July 8, 1955,

Serial No. 520,933

22 Claims. (Cl. 99-163) (Granted under Title 35, U. S. Code (1952), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, for governmental purposes,

throughout the world, with power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the stabilization of animal and vegetable fats and oils which are normally subject to oxidative deterioration, particularly such animal fats as lard and such vegetable or glyceride oils as cottonseed oil, soybean oil, and corn oil, and to such related materials as synthetically produced esters of long chain fatty acids, by incorporating therein novel additives thereby preventing such oxidative deterioration and consequently increasing the storage life and utility of such fatty substances.

This deterioration is mainly caused by autooxidative processes which are extremely difficult to control.

This invention is based upon the discovery that certain chemical compounds, when added to animal and vegetable fats and oils, particularly glyceride oils, in minor amounts, greatly increase the oxidative stability of the fats and oils. These compounds are disclosed and claimed in the copending application of John Hodge, Serial No. 512,915, filed June 2,1955.

As disclosed in the copending application, the stabiliz- R and R may be the same or a diflerent organic radical, such as alkyl, aryl, or aralkyl. iln addition, the two radicals A and R may be joined by an a'lkylene chain, such as in the piperi'dyl radical or by an oxygen interrupted alkylene chain such as the morpholinyl radical. The radicals R and R may be substituted by various radicals or substituents which are inert. One of the radicals R or R may also be hydrogen. Examples of particular substituents are ethyl, propyl, butyl, hexyl, hydroxypropyl, tolyl, benzyl, phenyl, and the like.

As disclosed in the copending application, the reductones and anhydro-reductones of this invention have 2 major portions of basic molecular structure, one of which is derived from an amine, HNRR, and the other derived from a reducing sugar, CnHZnOn. The former and latter interact to form a glycosylamine which, in turn, maybe rearranged into a deoxyaminoketose. This ketose may then be transformed by steps into amino-glycose-reductone and anhydro-amino-glycose-reductone by the process of the copending application. Suitable reducing sugars are heptoses, hexoses, pentoses, methyl .pentoses, deoxy sugars, amino sugars, sugar acids, tetroses, trioses, 'bioses and they may be aldoses or ketoses. Most important at present, economically speaking, are the aldohexoses such 25 as D-glucose, D-galactose or D-mannose, or ketohexoses such as D-fructose or L-sorbose.

The amine starting material may be any primary or secondary amine, including aliphatic, aromatic, aralkyl, lalicyclic and heterocyclic amines and amino acids.

'In the case of primary amines, such as ethanol-amine, benzylamine, a-phenylethyl-amine, 3-methoxypropylamine, glycine or alanine, the reductone is generally mi-crocrystalline or amorphous; whereas, in the case of secondary amines, macrocrystalline products are obtained. For the purpose of this invention, the reductones and anhydroreductones derived from secondary amines are preferred.

- Examples are piperidino-hexose-reductone, anhydro-pipermorpholino-hexose-reductone,

ing agents of this invention are amino-glycose-reductones and anhydro-amino-glycose-reductones, and they have the following general formulae.

Anhydro-amino-glycose-reductone idino-rednctone, morpholino-hexose-reductone, anhydro dimethylamino-hexose-reductone, anhydro-dimethylamino-hexose-reductone, di allylamino hexose reductone, anhydro diallylamino hexose-reductone, idi-nbutylamino hexose-reductone, anhydro-di-nbutylamino-hexose-reductone, piperazino di (hexose-reductone) and the like.

The following specific examples illustrate the invention.

EXAMPLE 1 A number of samples of cottonseed oil were placed in closed containers and treated with hexose-reductones as indicated in Table I. The samples were maintained at 60 C., and gaseous oxygen was introduced under pressure. At the periods shown by the various column headings, the quantity of oxygen absorbed by the oil was where n is an integer greater than -4 and less than 8, and

calculated from the changes in pressure, the value in each column being cumulative with the preceding values. A parallel control sample containing no additive was run, and the data is also recorded in Table I.

Table I.Oxygen absorption of reductone treated cottonseed oil [ML 02 absorbed per kg. 011 at 60 (1.]

Reductone 5 27 52 74 98 126 150 174 191 215 237 hours 1 hours hours hours hours hours hours hours hours hours hours 1. Control 107 200 343 466 657 937 1, 030 1, 067 2. .01% dimethylami110. 109 117 126 126 131 151 159 173 206 321 3. .01% anhydro dimethylamino..- 103 112 119 123 130 137 147 158 175 207 284 4. .01% piperidlno 98 106 114 123 131 142 153 181 257 388 547 5. .01% anhydro piperidino 107 121 128 135 142 150 160 185 230 6. 005% ascorbic acid plus 005% anhydro piperidino 115 128 137 1 1 190 305 450 630 760 1 Essentially amount of oxygen dissolved in the oil (unreacted).

As may be seen from Table I, there is a period during which very little oxygen is absorbed, and the rate of oxy gen uptakeis slow. The end of this'period, which may be t'eimed 'an induction period, 'is detectable as pronouiiced increase or break-point in the rate of oxygen uptak.- Table II shows" the break-points for this experiment. 'Table' II also sho'wsthe time required to reach a peroxide value of for each of the samples.

Tdble Ila-Break points of stabilized cottonseed oil With further regard to Table II it was interesting to find that the control oilreached a peroxide value of 20 in 48 hours, or a considerable time before any of the reductone-treated samples reached a-peroxide value of 20.

EXAMPLE 2 Samples of deodorized soybean oil, cottonseed oil, corn oil, hydrogenated soybeanoil, hydrogenated cottonseed oil, lard and undeodorized soybean oil were treated with Table HIQ-smbiliz evaluation as'indicat'ed by imam-5n various oxidation inhibitors or stabilizers, including those of this invention. The samples, including onecontrcfl for each substance which contained no stabilizer, were subjected to the oxygenating conditions of the Active" oxygen Method. Determination of peroxide values was inade periodically, and the titnes elapsed to'freacha peroxide value of 20 were observedf The results are given" inTableIII. 1 7

period determined by active oxygen method at 100 C. it

Time in hours toreach a peroxide value of20 Add1tives'Each at 0.01% concentration 7 Hydro Hydrop Unde- Soybean Cottbnom gamma 'genated Lard Lard Lard odorized 011 seedooll oil soybean ootton- II III soybean on seed oil oil 1. Control.-. 5.5 4.5 3. 5 32 5.5 2 Ascorbic ac 13 5.5 9.0 62 7.5 3. Ascorbyl palm ate 7' r 4.5 4. Citric aeid 10 4. 5 8.3 60' 96 8. 5 p 5. Propyl gallate l 4. 8 17. '4. 0 '144 2 72 A1 6. Sustane Six V r 1 25 7. Dlmethylamino reduetone"; 23 28 v 9.0 143 182 83 8. Diallylamino reductonen 17 18 I W I 49 9. Di-n-butylamino reductone- '65 10. Morpholiuo reductone 17 14 r 9.3 155 175 80. 11. Plperidino reduotone 19 18 6.3 .113. 1 168' Y 78 12. Dimethylamino reductone plus ascor- 1 1 I I p bio acid 33 31 '21 160' p 192 129 p 7 13. Dlmethylamino reductone plus citric I .i r afid 32 28 18 126 101 f 97 14. Dimethylamino reductone plus 7 propyl gallate I 21 .37 I i. .242. 145: l 15. Anhydro-dimethyl i110 redu 25 34 10', 185 -121 16. Anhydro-dimethylamino redueto t 'i 7 plus ascorbic acid 1 36 25.. 148 192 '145 i 17. Anhydro dirnethylamin plus citric acid 37 3 7 23 v 128 H 179 123 18. Anhydro-dimethylamino reductone I plus propylgallate. 25 250 196, 19. Anhydro-piperidino reductone 20 25 7.0' 133 165 83 20. Anhydro-piperidino 'reductone i M i" ascorbic acid -1. 32 32 21 161 21. Anhydro-piperidino reductone citric aci 29 27 is 140.. 105 11 22.Anhydro-piper1dino reductone plus propyl aall i 25 24$ 150 1 1 A cornrne'rc ial antioxidant containing 18 parts butylated hydroxyanisole @1122 parts butylated hydroiry toluene in 60 parts of cottdn seed 011.

* Peroxide value at the hours indicated is lesstnzm 1o.

Table VI.-Oxidative and organoleptic evolution of soybean oil stabilized with reductones After 4 days storage at 60 0.

Time womowwmwmwwwonmnmwwo 07170705031526272534 Peroxide value A. O. M.

Conditions 8 hr.

acid, or propylgallate show a surprising synergistic efiect in stabilizing lard. This efiect does not appear with the 5 g lard.

risin fatty materials other than those comp Reductone 0.01%

EXAMPLE 3 Samples of cottonseed oil were treated wi 0.01 per- 10 cent reductone in alcohol solution, and the alcohol removed by steam stripping at 100 C. for one hour.

dimethylamino.

(control) 1 anhydro piperi (control) anhydro di Portions were subjected to the active oxygen method (A. 0. M.) of the Swift stability test and the 8-hour gggg g g- A. O. M. values determined. Corresponding determinations were made on controls for each oil in which no stabilizer was added. The samples were subjected to a combined organoleptic and chemical evaluation. The former consisted of taste-testing by a panel of experienced di n-but y1amino analytical taste experts who graded the oils at each test on a scale of 0 to 10, the highest score corresponding to the blandest sample. At each tasting the peroxide values 2 (CQIItYOD of the samples were also determined. The results, aver- Steam stripped at 210 0. for 3 hours.

ages of several duplicate observations, are recorded in Table IV.

From the above table it may be seen that the reductone Table lV.-Organ0leptic and oxidative evaluations of cottonseed oil stabilized with reductones EXAMPLE 4 stabilizers impart considerable stability to the oils even The procedure of Example 3 was followed at hlgh and prolonged temperatures using instead samples of hydrogenated cottonseed oil. The re- EXAMPLE 6 Sults are gwen m Table Several reductones were dissolved in butter oil without the aid of solvents. Antioxygenic indices (AI) were obtained by the active oxygen method, the stability values being based on the number of hours required to reach a Table V.0rgan0leptic and oxidative evaluation of hydactones drogenated cottonseed oil stabilized with re The procedure of Example 4 was followed, using soybean oil. In the experiment half of the samples were ations (0.01%, 0.05%, and 0.10%) of di-octadecylsteam stripped at 210 C. for 3 hours as indicated in Table VI. a

an'lino-hexose-reductone. This reductone is a mixture of di-alkylamino-hexose-reductones, in which the alkyl groups are predominantly octadecyl groups. This reductone mixture was prepared according to the method disclosed in the prior application of Hodge, mentioned previously. In

the preparation, a commercially available mixture of long chain aliphatic secondary amines was used, made from tallow fatty acids.

Samples of the treated lard, together with an untreated control, were subjected to A. O. M. conditions. control a peroxide value of 20 Was reached in hours. At 8 hours it had increased to 100. In the treated samples, the peroxide values at the end of 8 hours were respectively, 5.2, 2.7, and 1.8. j v

In addition to the foregoing uses, the amino-glycosereductones of this invention are useful in preventing the oxidative deterioration in such fatty foods as margarine,

.cocoa, chocolate, bacon, fish, prepared meats, soups,

sandwich spreads, peanut butter, canned bread, nut meats, mayonnaise, French dressings, milk, ice cream and frozen desserts (melorine), dried, powdered, and frozen milks, dehydrated foods, deep-fat fried foods such as potato chips and doughnuts, frozen ready-to-serve meals, baby foods, cheese products, and the like. They are also useful in preserving essential oils, preserved fruits, candies, icings, coatings, chewing gum, vitamins in liquid or capsule form, cosmetics such as hand creams, face creams, soaps, lotions, perfumes, shampoos, animal feeds, inedible fats, paper for food wrapping or containers, gasoline, petroleum oils, turbine oil, lubricating oils, transformer oils, and the like.

What is claimed is:

1. A composition comprising .a material subject to oxidative deterioration and selected from the class consisting of fats and oils having incorporated therein a reductone selected from the group consisting of an aminoglycose-reductone and an anhydro-amino-glycose-reductone to stabilize said material against such deterioration.

2. A composition comprising a material subject to oxid'ative deterioration and selected from the class consisting of fats and oils having incorporated therein a reductone selected from the group consisting of an amino-glycosereductone having the formula CnH(2n5)O(n-3)NRR' and an anhydro-amino-glycose-reductone having the formula C1zH(2n-'7)O(n4)NRR' and wherein n is an integer greater than 4 and less than 8, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, a reductone of the above formulae in which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain, and a reductone of the above formulae in which n, R, and R have the same significance as above and in which R and R are joined by an oxygen interrupted alkylene chain to stabilize said material against such deterioration.

3. The composition of claim 2 wherein the material is an oil.

4. The composition of claim 3 wherein the oil is cottonseed oil.

5. The composition of claim 3 wherein the oil is soybean oil.

6. The composition of claim 3 wherein the oil is corn oil.

7. The composition of claim 2 wherein the material is a fat.

8. The composition of claim 7 wherein the fat is lard.

9. The composition of claim 2 in which the reductone is an amino-glycose-reductone having the formula C11.H(2n5)O(n3)NRR' wherein n is an integer greater than 4 and less than 8, R is a member selected'from the group consisting of an alykl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and and aralkyl radical, a reductone of the above formula in In the which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain, and a reductone of the above formula in which n, R, and R have the same significance as aboveand in which R and R are joined by an oxygen interrupted alkylene chain.

10. The composition of claim 9 wherein the reductone is a dimethylamino-hexose-reductone.

11. The composition of claim 9 wherein the reductone is a piperidino-hexose reductone. 7

12. The composition of claim 2 in which the reductone is an anhydro-amino-glycose-reductone having the formula CnH' 2n-'z O(n 4 NRR wherein n is an integer greater than 4 and less than 8, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an 'alkyl radical, an aryl radical, and an aralkyl radical, a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain and a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an oxygen interrupted alkylene chain.

13. The composition of claim 12 wherein the reductone is an anhydro-dimethylamino-hexosereductone.

14. The composition of claim 12 wherein the reductone is an anhydro-piperidino-hexosereductone.

15. A composition stabilized against oxidative deterioration comprising lard having incorporated therein a member selected from the group consisting of ascorbic acid, citric acid, and propyl gallate, and a reductone selected from the group consisting of an amino-glycosereductone and an anhydro-amino-glycose-reductone.

16. A compositionstabilized against oxidative deterioration comprising lard having incorporated therein a member selected from the group consisting of ascorbic acid, citric acid, and propyl gallate, and a reductone selected from the group consisting of an amino-glycose reductone having the formula CnH 2n 5 O 1t-3 NRR and an anhydro-amino-glycose-reductone having the formula CnH zn-'z O n-4 NRR and wherein n is an integer greater than 4 and less than 8, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain, and a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an oxygen interrupted alkylene chain.

17. The composition of claim 16 in which the reductone is an amino-glycose-reductone having the formula CnH(2n-5 O n -3 NRR wherein n is an integer greater than 4 and less than 8, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain, and a reductone of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an oxygen interrupted alkylene chain.

18. The composition of claim 17 wherein the reductone is a dimethylamino-hexose-reductone.

19. The composition of claim 17 wherein the reductone is a piperidino-hexose-reductone.

20. The composition of claim 16 in which the reductone is an anhydro-amino-glycose-reductone having the formula CnH(2n-7)O(,n4)NRR' wherein n is an integer greater than 4 and less than 8, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, R is a member selected from the group consisting of an alkyl radical, an aryl radical, and an aralkyl radical, a rednct-one of the above formula in which n, R, and R have the same significance as above and in which R and R are joined by an alkylene chain, an a reductone of the above formula in which n, R and R have the same significance as above and in which R and R are joined by an oxygen interrupted alkylene chain.

10 21. The composition of claim 20 wherein the reductone is an anhydro-dirnethylamino-hexose-reductone.

22. The composition of claim 20 wherein the reductone is an anhydro-piperidino-heXose-reductone. 5

References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMPOSITION COMPRISING A MATERIAL SUBJECT TO OXIDATIVE DETERIORATION AND SELECTED FROM THE CLASS CONSISTING OF FATS AND OILS HAVING INCORPORATED THEREIN A REDUCTONE SELECTED FROM THE GROUP CONSISTING OF AN AMINOGLYCOSE REDUCTONE AND AN ANHYDRO-AMINO-GLYCOSE-REDUCTONE TO STABILIZE SAID MATERIAL AGAINST SUCH DETERIORATION. 